Photographic material with improved surface properties

ABSTRACT

Photographic materials comprising a support, a light-sensitive silver halide emulsion layer on said support and thereover a hydrophilic colloidal protective coating is described. The photographic material will include resorcin in the emulsion layer and a poly-N-vinyl lactam or polyvinyl lactone in the emulsion layer or in the protective surface coating. The surface coating will include silica particles and a polycarbocyclic aromatic sulphonic acid or water-soluble salt thereof. The photographic material is free or substantially free from milkiness or cloudiness normally associated with photographic materials comprising resorcin, polyvinyllactam or polyvinyllactone, and silica.

nited States Patent Thiers et a1.

15] 3,6563% [45] Apr. 18, 1972 PHOTOGRAPHIC MATERIAL WITH IMPROVED SURFACE PROPERTIES Inventors: Robrecht Julius Thiers, Brasschaat; Jozef Frans Willems, Wilrijk, both of Belgium Assignee: Gevaert-AGFA N.V., Mortsel, Belgium Filed: Aug. 26, 1969 Appl. No.: 853,211

Foreign Application Priority Data Mar. 17,1969 Great Britain ..13,884/69 References Cited UNITED STATES PATENTS l-leckelmann ..96/ 87 Meerkamper ..96/67 6/1965 Koerber ..96/82 3,380,828 4/1968 Kitze ..96/66 FOREIGN PATENTS OR APPLICATIONS 220,186 3/1967 U.S.S.R ..96/50 PL Primary Examiner-Norman G. Torchin Assistant Examiner-Judson R. l-lightower Attarney-A1fred W. Brenier [57] ABSTRACT Photographic materials comprising a support, a light-sensitive silver halide emulsion layer on said support and thereover a hydrophilic colloidal protective coating is described. The photographic material will include resorcin in the emulsion layer and a poly-N-vinyl lactam or polyvinyl lactone in the emulsion layer or in the protective surface coating. The surface coating will include silica particles and a polycarbocyclic aromatic sulphonic acid or water-soluble salt thereof.

The photographic material is free or substantially free from milkiness or cloudiness normally associated with photographic materials comprising resorcin, polyvinyllactam or polyvinyllactone, and silica.

' 19 Claims, No Drawings The present invention relates to photographic light-sensitive material with improved surface properties.

It is generally known in the photographic art to use lightsensitive silver halide material containing finely divided silica particles in the outer layer. Silica particles are incorporated in the outer layer of the photographic material for all kinds of purposes. For instance, it has been proposed to include finely divided silica particles in the outer layer of a photographic material in order to reduce the sticking tendency of said material for example when the material is stored or packed in the form of a roll or stack. The roughness produced by the silica particles atthe surface of the photographic material also prevents the generation of static electricity, which causes sparks and thus exposure of the photographic material, as well as the formation of Newtons rings when printing and enlarging in that the contact surface of said material with another material is relatively small. Further, the outer layer with silica particles also very noticeably decreases abrasion by dry-friction and reduces the tendency of scratching when materials are stored or packed in contact with other material as is the case, e.g., with X-ray material packed without interleaves (non interleaved fold-scratching or NIF-scratching).

However, the use of silica particles in a surface coating, e.g., a protective coating applied to the light-sensitive silver halide emulsion layer of a photographic material, also presents a number of drawbacks. For instance it has been observed that the presence of silica particles in a protective hydrophilic colloid surface coating of a photographic material comprising resorcin in a light-sensitive silver halide emulsion layer and a polyvinyl lactam or polyvinyl lactone such as poly-N-vinylpyrrolidone and polyvinyl-Z-oxazolidine in the said surface coating, has an unfavorable efiect on the slight unobjectionable milky appearance of the material caused by the presence of the said resorcin and the said polyvinyl compound in that the milkiness or cloudiness is now much more pronounced and visible even in the processed material whichis quite undesirable, especially in transparent photographic materials.

It has now been found that in a photographic material comprising a support, a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid protective surface coating, which is provided at the same side of the support as the said emulsion layer and comprises dispersed therein silica particles, the milkiness or cloudiness produced by the presence in the said photographic material of resorcin and a polyvinyl lactam or polyvinyl lactone, can be materially reduced or eliminated by incorporating in said surface coating, in addition to the silica particles a polycarbocyclic aromatic (as hereinafter defined) sulphonic acid or a water-soluble salt thereof.

The term polycarbocyclic aromatic as used herein is intended to mean two or more benzene rings fused together (for example, as in naphthalene, pyrene and dibenzothiophene dioxide), or at least two aromatic rings directly joined together (for example as in diphenyl or terphenyl) or joined through the intermediary of an aliphatic group, e.g., alkylene and alkenylene, which may be interrupted by one or more hetero atoms, e.g., a bisamido group derived from aliphatic or aromatic dicarboxylic acids such as phthalamido.

The sulphonated compounds of use according to the present invention can be represented by the following formula I:

R-s0,M r.

M is hydrogen, a metal atom such as sodium and potassium,

or ammonium. Particularly useful compounds corresponding to the above general formula I, can be represented by the following formula:

wherein: v

M has the same significance as above,

B stands for hydrogen, a fused aromatic ring including a substituted aromatic ring such as sulphonated benzo, an amino group including a substituted amino group, preferably an amide or a s-triazin-Z-ylamino group,

A stands for alkylene such as ethylene, alkenylene, such as CH 3 CH- or a bisamido group such as HNCO R-CONH- wherein R stands for alkylene or arylene for example phthalamido, and

B stands for an aromatic group including a substituted aromatic group, preferably the group Sulphonated compounds wherein B is as-triazin-Z-ylamino group, are for instance, those corresponding to the following general formula:

M has the same significance as above.

X stands for CH CH or Chg-CH2, and

each of Z, and Z stands for s-triazin-Z-yl including substituted s-triazin-2-yl, e.g., substituted by hydroxyl, aryloxy (e.g,, phenoxy, o-toloxy, p-sulphophenoxy, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), a halogen atom (e.g., chlorine, bromine, etc.), a heterocyclic radical (e.g., morpholinyl, piperidyl, etc.), an alkylthio group (e.g., methylthio, ethylthio, etc.), an arylthio group (eg phenylthio, tolylthio, etc.), a heterocyclylthio group (e.g., benzothiazylthio, etc.), an amino group, an alkylamino group (e.g., methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino, cyclohexylamino, B-hydroxyethylamino, di-B-hydroxyethylamino, B-sulphoethylamino, etc.), an arylamino group (e.g., anilino, o-, m-, and p-sulpho-anilino, 0-, m-, and pchloroanilino, o-, m-, and panisylamino, o-, m-, and ptoludino, o-, m-, and p-carboxyanilino, hydroxyanilino, sulphonaphthylamino, o-, m-, and p-aminoanilino-pacetamidoanilino, etc.), etc.

The bistriazyl aminostilbene compounds corresponding to general formula III, which are especially useful in practicing our invention have been previously employed in the art as fluorescent agents and as bleaching (optical) agents as well as in the textile industry and hence are widely known substances.

Representative examples of compounds of use according to the present invention are:

\C% S O Na S OaNa HO-CHz-CHz N 5. S O3N3 S 03H S 0 H OrNa S OaNa N CHrCHz-OH CHz-CHz-OH s 03H s 0311 Thus, in accordance with the present invention there is provided a photographic silver halide material comprising in one of its hydrophilic colloid layers resorcin and in the same or other hydrophilic colloid layer a polyvinyl lactam or lactone wherein said material is provided with a non-light-sensitive hydrophilic colloid surface layer, which is coated at the same side of the support as the silver halide emulsion layer(s) of the said material and comprises in addition to dispersed silica particles a polycarbocyclic aromatic sulphonic acid or watersoluble salt thereof as defined above.

The invention is of particular value in the manufacture of X- ray material and other double coated films where both sides of the film support, e.g., a cellulose triacetate or polyethylene terephthalate film support, are provided with light-sensitive silver halide emulsion layers and hydrophilic colloid protective surface layers as outer layers.

The silica particles of use according to the present invention preferably have an average particle size of less than 1 micron, more especially from about 0.01 to about 0.2 micron. They are incorporated into the hydrophilic colloid coating composition of the outer layer from aqueous dispersions or suspensions of silica. Aqueous suspensions of silica that have been found particularly effective comprise those marketed by Monsanto Chemical Corporation, Boston, Mass, U.S.A. under the description SYTON such as SYTON W-" and SYTON 2-X and by E. l. du Pont de Nemours & Co., Wilmington, Del., U.S.A. under the description LUDOX such as LU- DOX LS.

SYTON W-20 is a trade name for a 15 percent aqueous suspension of silicium dioxide having an average particle size of 0.14 micron. SYTON 2-X is a trade name for a percent aqueous suspension of silicium dioxide having an average particle size of 0.025 micron. LUDOX LS is a trade name for a 30 percent aqueous suspension of silicium dioxide having an average particle size of 0.015 micron.

The amount of aqueous suspension of silica added to the coating composition of the outer layer is preferably such that from about 0.1 g to about 1 g, more especially from 0.25 to 0.75 g, of silicon dioxide is present per sq.m.

The polycarbocyclic aromatic sulphonic acids or watersoluble salts thereof used in accordance with the present invention are preferably incorporated into the coating composition of the outer layer from aqueous solutions. They are generally used in amounts comprised between 1 mg and mg per sq.m, preferably between 5 mg and 30 mg per sq.m.

The use of the polyvinyl lactam and lactone compounds such as poly-N-vinylpyrollidone and polyvinyl-2-oxazolidone in photographic material is generally known in the art. These compounds can be used as antifoggants in a light-sensitive silver halide emulsion layer or another water-permeable colloid layer of the photographic material. In accordance with the present invention they are preferably used in the hydrophilic colloid protective surface coating in amounts generally comprised between 0.02 g and l g per sq.m. The polyvinyl lactone or polyvinyl lactam may also function as hydrophilic colloid binder for the water-permeable colloid coatings, e.g., the protective or antistress outer colloid coating of the photographic material. Indeed, though gelatin is preferably used as hydrophilic colloid binder for the water-permeable colloid layers of photographic material other suitable natural or synthetic hydrophilic colloids may wholly or partly replace the gelatin, e.g., casein, zein, colloidal albumin, a cellulose derivative such as carboxymethylcellulose, polyvinylalcohol, poly- N-vinyl-pyrrolidone, etc.

The hydrophilic colloid composition for the protective coating may, of course, comprise in addition to the silica-particles and the polycarbocyclic aromatic sulphonic acid or watersoluble salt thereof, all sorts of other ingredients such as wetting agents, plasticizers, hardeners, antistatic agents, etc.

The use of resorcin in photographic silver halide material layers is also generally known in the art. It is commonly used as hardening accelerator for aldehyde hardeners, such as formaldehyde whereby the unfavourable effect of the aldehyde on the sensitometric characteristics such as increase of fog is reduced or eliminated. In accordance with the present invention the resorcin is preferably used in the silver halide emulsion layer in amounts generally comprised between 1 g and 15 g per kg of emulsion.

As noted above, the hydrophilic colloid protective coating comprising silica particles and in addition thereto a polycarboresorcin and a said polyvinyl compound. The emulsion layers may be spectrally sensitized or non-sensitized emulsion layers. They may be high-sensitive negative emulsions as well as rather low sensitive positive emulsions.

Various silver salts may be used as light-sensitive salt, e.g., silver bromide, silver iodide, silver chloride or mixed silver halides, e.g., silver chlorobromide or silver bromoiodide. These silver halides are dispersed in the common hydrophilic colloids or mixtures of colloids, examples of which are given above, gelatin being, however, favored.

The support may be any conventional transparent or opaque support as normally used in the art such as paper, glass and film. The invention, however, is of particular advantage in those cases where transparent film supports are used such as films of cellulose esters for instance cellulose triacetate, and films of polyesters for instance polyethylene terephthalate.

The following example illustrates the present invention.

EXAMPLE A gelatino silver bromoiodide (2 mole percent of iodide) emulsion containing resorcin and comprising per kg 76 g of gelatin and an amount of silver halide corresponding to 190 g of silver nitrate, is coated on both sides of a subbed cellulose triacetate support pro rata of about 25 sq.m per kg of emulsron.

To the emulsion layer, which is still wet, a gelatin antistress layer is applied from an aqueous gelatin composition comprising per liter 30 g of gelatin, 28 ml of a 20 percent aqueous solution of polyvinylpyrrolidone, 40 ml of SYTON 2X (trade name) and m1 of a 4 percent aqueous solution of compound l. The gelatin antistress layer is coated pro rata of about 27 sq.m per liter of aqueous gelatin composition, which means that per sq.m about 1.1 g of gelatin, 0.2 g of polyvinylpyrrolidone, 0.44 g of silica and mg of compound 1 are present.

When comparing the material thus formed with a material prepared in an analogous way but comprising no compound 1 it was found that the latter material contrary to the material according to the invention has an undesirable milky appearance.

The same favorable effect was obtained with a material prepared as described above wherein, in the gelatin antistress layer the compound 1 was replaced by a same amount of compound 5.

We claim:

1. A photographic material comprising a support carrying a light-sensitive silver halide emulsion layer and thereover a hydrophilic colloid protective surface coating, said photographic material comprising resorcin in said emulsion layer and a poly-N-vinyllactarn or polyvinyl lactone in said emulsion layer or in said surface coating, said surface coating further including silica particles and a polycarbocyclic aromatic sulphonic acid or water-soluble salt thereof, said material salt thereof is a compound corresponding to the formula:

wherein:

10 M stands for hydrogen, a metal atom or ammonium,

wherein:

M stands for hydrogen, a metal atom or ammonium,

X stands for CH CH or Cl-h-Cl-l and each of Z and Z stands for a s-triazin-Z-yl group.

4. A photographic material according to claim 1, wherein the said resorcin is present in a light-sensitive silver halide emulsion layer.

5. A photographic material according to claim 1, wherein the poly-N-vinyllactam or polyvinyllactone is present in the said non-light-sensitive hydrophilic colloid protective surface coating.

6. A photographic material according to claim 1, wherein the poly-N-vinyl lactam is poly-N-vinylpyrrolidone;

7. A photographic material according to claim 1, wherein the polyvinyllactone is polyvinyl-Z-oxazolidone.

8. A photographic material according to claim 1, wherein the average particle size of the silica is less than 1 micron.

9. A photographic material according to claim 8, wherein the average particle size of the silica is comprised between 0.01 and 0.2 micron.

10. A photographic material according to claim 1, wherein the polycarbocyclic aromatic sulphonic acid or a water-soluble salt thereof is present in the said surface coating in an amount comprised between 1 mg and mg per sq. m.

11. A photographic material according to claim 1, wherein the hydrophilic colloid of the said surface coating is gelatin.

12. A photographic material according to claim 1, wherein the said silver halide emulsion layer is a gelatino silver halide X-ray emulsion layer.

13. A photographic material according to claim 1, wherein the said material is a double-coated X-ray film material provided at both sides of the film support with a said light-sensitive silver halide emulsion layer and a said hydrophilic protective surface coating.

14. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:

being free or substantially free from milkiness or cloudiness.

2. A photographic material according to claim 1, wherein said polycarbocyclic aromatic sulphonic acid or water-soluble 15. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:

N N Cy OgNB OaNa I All OH 16. A photographic material according to claim 1, wherein to the formula:

the said polycarbocyclic aromatic sulphonic acid corresponds l S OaNa s O Na to the formula: l

fiNIP-O c -c O-NH W N U HOCHQCH2NHC CNH@CH= l 1 Q I s OaNa S 1 s 19. A photographic material according to claim 1, wherein i 2 the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:

17. A photographic material according to claim 1, wherein HzN cH2-cm I -Nm the said polycarbocyclic aromatic sulphonic acid corresponds to the formula: s 03H s 03H HO-CHr-CH: N N CHz-CHz-OH 18. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds 

2. A photographic material according to claim 1, wherein said polycarbocyclic aromatic sulphonic acid or water-soluble salt thereof is a compound corresponding to the formula: wherein: M stands for hydrogen, a metal atom or ammonium, B1 stands for hydrogen, fused-on-carbocyclic aromatic ring or an amino group, A stands for an alkylene group, an alkenylene group or a bisamido group, and B2 stands for an aromatic group.
 3. A photographic material according to claim 2, wherein said compound corresponds to the formula: wherein: M stands for hydrogen, a metal atom or ammonium, X stands for CH=CH or CH2-CH2, and each of Z1 and Z2 stands for a s-triazin-2-yl group.
 4. A photographic material according to claim 1, wherein the said resorcin is present in a light-sensitive silver halide emulsion layer.
 5. A photographic material according to claim 1, wherein the poly-N-vinyllactam or polyvinyllactone is present in the said non-light-sensitive hydrophilic colloid protective surface coating.
 6. A photographic material according to claim 1, wherein the poly-N-vinyl lactam is poly-N-vinylpyrrolidone.
 7. A photographic material according to claim 1, wherein the polyvinyllactone is polyvinyl-2-oxazolidone.
 8. A photographic material according to claim 1, wherein the average particle size of the silica is less than 1 micron.
 9. A photographic material according to claim 8, wherein the average particle size of the silica is comprised between 0.01 and 0.2 micron.
 10. A photographic material according to claim 1, wherein the polycarbocyclic aromatic sulphonic acid or a water-soluble salt thereof is present in the said surface coating in an amount comprised between 1 mg and 100 mg per sq. m.
 11. A photographic material according to claim 1, wherein the hydrophilic colloid of the said surface coating is gelatin.
 12. A photographic material according to claim 1, wherein the said silver halide emulsion layer is a gelatino silver halide X-ray emulsion layer.
 13. A photographic material according to claim 1, wherein the said material is a double-coated X-ray film material provided at both sides of the film support with a said light-sensitive silver halide emulsion layer and a said hydrophilic protective surface coating.
 14. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:
 15. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:
 16. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:
 17. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:
 18. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula:
 19. A photographic material according to claim 1, wherein the said polycarbocyclic aromatic sulphonic acid corresponds to the formula: 